Fungicidal fused bicyclic pyrimidinones

ABSTRACT

A method for controlling wheat powdery mildew is provided which encompasses applying to the plant, seed, seedling or portion of the plant to be protected, or, to its growing media, an effective amount of a compound of Formula II                    
     where Q is O, n is 0, R 3  is halogen, R 4  is halogen or hydrogen, R 5  is an alkyl group having from three to five carbon atoms and R 6  is an alkyl group having from three to eight carbon atoms. Also provided are certain compositions for controlling wheat powdery mildew which contain a compound of Formula II together with a surfactant, an organic solvent and/or a solid or liquid diluent. Also provided are certain fungicidal compounds within Formula II for controlling wheat powdery mildew.

This application is a division of U.S. patent application No. 09/007,336, filed Jan. 14, 1998 now U.S. Pat. No. 5,945,423 which is a continuation of U.S. patent application No. 08/545,827, now U.S. Pat. No. 5,747,497, filed Nov. 8, 1995, the national filing under 35 USC 371 of International Application No. PCT/US94/04965 filed May 10, 1994 claiming priority, in part, of U.S. patent application No. 08/144,904 filed Oct. 28, 1993 and U.S. patent application No. 08/060,629 filed May 12, 1993.

This invention relates to certain 4(3H)quinazolinones, their agriculturally suitable salts and compositions, and methods of their use as general or selective fungicides, in particular for the control of cereal powdery mildew both preventive and curative.

U.S. Pat. No. 3,755,582 and U.S. Pat. No. 3,867,384 disclose certain 4(3H)-quinazolinone fungicides. These patents, however, do not specifically disclose the compounds of the present invention.

SUMMARY OF THE INVENTION

This invention comprises compounds of Formulae I, II, and III including all geometric and stereoisomers, N-oxides, agriculturally-suitable salts thereof, agricultural compositions containing them and their use as fungicides:

wherein:

n is 0, 1 or 2;

Q is independently O or S;

R¹ is C₃-C₁₀ alkyl; C₃-C₅ cycloalkyl; C₄-C₁₀ alkenyl; C₄-C₁₀ alkynyl; C₁-C₁₀ haloalkyl; C₃-C₁₀ haloalkenyl; C₃-C₁₀ haloalkynyl, C₂-C₁₀ alkoxyalkyl; C₂-C₁₀ alkylthioalkyl; C₂-C₁₀ alkylsulfinylalkyl; C₂-C₁₀ alkylsulfonylalkyl; C₅-C₁₀ cycloalkylalkyl; C₄-C₁₀ alkenyloxyalkyl; C₄-C₁₀ alkynyloxyalkyl; C₄-C₁₀ (cycloalkyl)oxyalkyl; C₄-C₁₀ alkenylthioalkyl; C₄-C₁₀ alkynylthioalkyl; C₆-C₁₀ (cycloalkyl)thioalkyl; C₂-C₁₀ haloalkoxyalkyl; C₄-C₁₀ haloalkenyloxyalkyl; C₄-C₁₀ haloalkynyloxyalkyl; C₄-C₁₀ alkoxyalkenyl; C₄-C₁₀ alkoxyalkynyl; C₄-C₁₀ alkylthioalkenyl; C₄-C₁₀ alkylthioalkynyl; C₄-C₁₀ trialkylsilylalkyl; C₁-C₁₀ alkyl substituted with NR¹¹R¹², nitro, cyano, or phenyl optionally substituted with R¹⁴, R¹⁵, and R¹⁶; C₁-C₁₀ alkoxy; C₁-C₁₀ haloalkoxy; C₁-C₁₀ alkylthio; C₁-C₁₀ haloalkylthio; NR¹¹R¹²; or pyridyl, furanyl, thienyl, naphthyl, benzofuranyl, benzothienyl, or quinolinyl each optionally substituted with R¹⁴, R¹⁵, and R¹⁶;

R² is C₃-C₁₀ alkyl, C₆-C₇ cycloalkyl; C₃-C₁₀ alkenyl; C₃-C₁₀ alkynyl; C₁-C₁₀ haloalkyl;, C₃-C₁₀ haloalkenyl; C₃-C₁₀ haloalkynyl; C₂-C₁₀ alkoxyalkyl; C₂-C₁₀ alkylthioalkyl; C₂-C₁₀ alkylsulfinylalkyl; C₂-C₁₀ alkylsulfonylalkyl; C₄-C₁₀ cycloalkylalkyl; C₄-C₁₀ alkenyloxyalkyl; C₄-C₁₀ alkynyloxyalkyl; C₄-C₁₀ (cycloalkyl)oxyalkyl; C₄-C₁₀ alkenylthioalkyl; C₄-C₁₀ alkynylthioalkyl; C₆-C₁₀ (cycloalkyl)thioalkyl; C₂-C₁₀ haloalkoxyalkyl; C₄-C₁₀ haloalkenyloxyalkyl; C₄-C₁₀ haloalkynyloxyalkyl; C₄-C₁₀ alkoxyalkenyl; C₄-C₁₀ alkoxyalkynyl; C₄-C₁₀ alkylthioalkenyl; C₄-C₁₀ alkylthioalkynyl; C₄-C₁₀ trialkylsilylalkyl; C₃-C₁₀ cyanoalkyl; C₂-C₁₀ nitroalkyl; C₁-C₁₀ alkyl substituted with CO₂R¹¹, NR¹¹R¹², or phenyl optionally substituted with R¹³, R¹⁵, and R¹⁶; phenyl optionally substituted with R¹³, R¹⁵, and R¹⁶; —N=CR¹¹R¹¹; or —NR¹¹R¹²; or

R¹ and R² are taken together to form —CH₂(CH₂)_(m)CH₂—;

m is 1-4;

R³ is halogen; C₁-C₈ alkyl; C₃-C₈ cycloalkyl; C₂-C₈ alkenyl; C₂-C₈ alkynyl; C₁-C₈ haloalkyl; C₃-C₈ haloalkenyl; C₃-C₈ haloalkynyl; C₁-C₈ alkoxy; C₁-C₈ haloalkoxy; C₃-C₈ alkenyloxy; C₃-C₈ alkynyloxy; C₁-C₈ alkylthio; C₃-C₈ alkenylthio; C₃-C₈ alkynylthio; C₁-C₈ alkylsulfinyl; C₁-C₈ alkysulfonyl; C₂-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₂-C₈ alkylsulfinylalkyl; C₂-C₈ alkylsulfonylalkyl; C₄-C₈ cycloalkylalkyl; C₃-C₈ trialkylsilyl; nitro; NR¹¹R¹²; C₅-C₈ trialkylsilylalkynyl; or phenyl optionally substituted with at least one R¹³.

R⁴ is hydrogen; halogen; C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₁-C₄ alkoxy; or C₁-C₄ haloalkoxy;

R⁵ is C₃-C₅ alkyl; C₇-C₁₀ alkyl; C₄-C₇ alkenyl; C₃-C₅ alkynyl; C₁-C₁₀ haloalkyl; C₅-C₁₀ haloalkenyl; C₃-C₁₀ haloalkynyl; C₂-C₁₀ alkoxyalkyl other than methoxypropyl; C₂-C₁₀ alkylthioalkyl; C₂-C₁₀ alkylsulfinylalkyl; C₂-C₁₀ alkylsulfonylalkyl; C₄-C₁₀ cycloalkylalkyl; C₄-C₁₀ alkenyloxyalkyl; C₄-C₁₀ alkynyloxyalkyl; C₄-C₁₀ (cycloalkyl)oxyalkyl; C₄-C₁₀ alkenylthioalkyl; C₄-C₁₀ alkynylthioalkyl; C₆-C₁₀ (cycloalkyl)thioalkyl; C₂-C₁₀ haloalkoxyalkyl; C₄-C₁₀ haloalkenyloxyalkyl; C₄-C₁₀ haloalkynyloxyalkyl; C₄-C₁₀ alkoxyalkenyl; C₄-C₁₀ alkoxyalkynyl; C₄-C₁₀ alkylthioalkenyl; C₄-C₁₀ alkylthioalkynyl; C₄-C₁₀ trialkylsilylalkyl; C₁-C₁₀ alkyl substituted with NR¹¹R¹², nitro, or phenyl optionally substituted with at least one of R¹⁴, R¹⁵, and R¹⁶; C₂-C₁₀ alkyl substituted with cyano; C₁-C₁₀ alkoxy; C₁-C₁₀ haloalkoxy; C₁-C₁₀ alkylthio; C₁-C₁₀ haloalkylthio; NR¹¹R¹²; or phenyl, furanyl, thienyl, naphthyl, benzofuranyl, or benzothienyl each optionally substituted with R¹⁴, R¹⁵, and R¹⁶;

R⁶ is C₃-C₁₀ alkyl: C₃-C₇ alkenyl; C₃-C₁₀ alkynyl, C₁-C₁₀ haloalkyl; C₃-C₁₀ haloalkenyl; C₃-C₁₀ haloalkynyl; C₃-C₁₀ alkoxyalkyl other than propoxymethyl; C₂-C₁₀ alkylthioalkyl; C₂-C₁₀ alkylsulfinylalkyl; C₂-C₁₀ alkylsulfonylalkyl; C₄-C₁₀ cycloalkylalkyl; C₄-C₁₀ alkenyloxyalkyl; C₄-C₁₀ alkynyloxyalkyl; C₄-C₁₀ (cycloalkyl)oxyalkyl; C₄-C₁₀ alkenylthioalkyl; C₄-C₁₀ alkynylthioalkyl; C₆-C₁₀ (cycloalkyl)thioalkyl; C₂-C₁₀ haloalkoxyalkyl; C₄-C₁₀ haloalkenyloxyalkyl; C₄-C₁₀ haloalkynyloxyalkyl; C₄-C₁₀ alkoxyalkenyl; C₄-C₁₀ alkoxyalkynyl; C₄-C₁₀ alkylthioalkenyl; C₄-C₁₀ alkylthioalkynyl; C₄-C₁₀ trialkylsilylalkyl; C₅-C₁₀ cyanoalkyl; C₂-C₁₀ nitroalkyl; or C₃-C₁₀ alkyl substituted with CO₂R¹¹, NR¹¹R¹², or phenyl optionally substituted with R¹³, R¹⁵, and R¹⁶; or phenyl optionally substituted with R¹³, R¹⁵, and R¹⁶; or

R⁵ and R⁶ are taken together to form —CH₂(CH₂)_(m)CH₂—;

R⁷ is C₃-C₁₀ alkyl; C₃-C₇ cycloalkyl; C₄-C₇ alkenyl; propynyl; C₅-C₁₀ alknyl; C₂-C₁₀ haloalkyl; C₃-C₁₀ haloalkenyl; C₃-C₁₀ haloalkynyl; C₂-C₁₀ alkoxyalkyl; C₂-C₁₀ alkylthioalkyl; C₂-C₁₀ alkylsulfinylalkyl; C₂-C₁₀ alkylsulfonylalkyl; C₄-C₁₀ alkenyloxyalkyl; C₄-C₁₀ alkynyloxyalkyl; C₄-C₁₀ (cycloalkyl)oxyalkyl; C₄-C₁₀ alkenylthioalkyl; C₄-C₁₀ alkynylthioalkyl; C₆-C₁₀ (cycloalkyl)thioalkyl; C₂-C₁₀ haloalkoxyalkyl; C₄-C₁₀ haloalkenyloxyalkyl; C₄-C₁₀ haloalkynyloxyalkyl; C₄-C₁₀ alkoxyalkenyl; C₄-C₁₀ alkoxyalkynyl; C₄-C₁₀ alkylthioalkenyl; C₄-C₁₀ alkylthioalkynyl; C₄-C₁₀ trialkylsilylalkyl; C₁-C₁₀ alkyl substituted with NR¹¹R¹² or nitro; C₂-C₁₀ alkyl substituted with cyano; C₁-C₁₀ alkoxy; C₁-C₁₀ haloalkoxy; C₁-C₁₀ alkylthio; C₁-C₁₀ haloalkylthio; NR¹²R¹⁷; or phenyl, pyridyl, furanyl, thienyl, naphthyl, benzofuranyl, benzothienyl, or quinolinyl each optionally substituted with R¹⁴, R¹⁵, and R¹⁶;

R⁸ is hydrogen; C₁-C₄ alkyl; or —C(=O)R¹⁰;

R⁹ is hydrogen; C₂-C₁₀ alkyl; C₃-C₇ cycloalkyl; C₃-C₁₀ alkenyl; C₃-C₁₀ alkynyl; C₃-C₁₀ haloalkyl; C₃-C₁₀ haloalkenyl; C₃-C₁₀ haloalknyl; C₃-C₁₀ alkoxyalkyl other than butoxyethyl; C₂-C₁₀ alkylthioalkyl; C₂-C₁₀ alkylsulfinylalkyl; C₂-C₁₀ alkylsulfonylalkyl; C₄-C₁₀ cycloalkylalkyl; C₄-C₁₀ alkenyloxyalkyl; C₄-C₁₀ alkynyloxyalkyl; C₄-C₁₀ (cycloalkyl)oxyalkyl; C₄-C₁₀ alkenylthioalkyl; C₄-C₁₀ alkynylthioalkyl; C₆-C₁₀ (cycloalkyl)thioalkyl; C₂-C₁₀ haloalkoxyalkyl; C₄-C₁₀ haloalkenyloxyalyl; C₄-C₁₀ haloalkynyloxyalkyl; C₄-C₁₀ alkoxyalkenyl; C₄-C₁₀ alkoxyalkynyl; C₄-C₁₀ alkylthioalkenyl; C₄-C₁₀ alkylthioalkynyl; C₄-C₁₀ trialkylsilylalkyl; C₁-C₁₀ alkyl substituted with NR¹¹R¹²; C₄-C₁₀ cyanoalkyl; C₂-C₁₀ nitroalkyl; C₁-C₈ alkyl substituted with CO₂R¹¹; pyridyl, furanyl, thienyl, or naphthyl each optionally substituted with R¹⁴, R¹⁵, and R¹⁶; —N=CR¹¹R¹¹; —NR¹²R¹⁷; —OR¹²; or —NC(=Q)NR¹¹R¹²; or R³ and R⁴ are both iodine and R⁹ is phenyl optionally substituted with R¹⁴, R¹⁵, and R¹⁶; or

R⁷ and R⁹ are taken together to form —CH₂(CH₂)_(m)CH₂—;

R¹⁰ is hydrogen; C₁-C₄ alkyl; C₁-C₄ alkoxy; or NR¹¹R¹²;

R¹¹ is independently hydrogen; C₁-C₄ alkyl; or phenyl optionally substituted with at least one R¹³;

R¹² is independently hydrogen; C₁-C₈ alkyl; or phenyl optionally substituted with at least one R¹³; or

R¹¹ and R¹² are taken together to form —CH₂CH₂CH₂CH₂—, —CH₂(CH₂)₃CH₂—, —CH₂CH₂OCH₂CH₂—, —CH₂CH(Me)CH₂CH(Me)CH₂—, or —CH₂CH(Me)OCH(Me)CH₂—;

R¹³ is independently halogen; C₁-C₄ alkyl; C₁-C₄ alkoxy; C₁-C₄ haloalkyl; nitro; or cyano;

R¹⁴ is independently C₁-C₆ alkyl; C₁-C₆ alkoxy; C₁-C₆ haloalkyl; halogen; C₂-C₈ alkynyl; C₁-C₆ thioalkyl; phenyl or phenoxy each optionally substituted with at least one R¹³; cyano; nitro; C₁-C₆ haloalkoxy; C₁-C₆ haloalkylithio; C₂-C₆ alkenyl; C₂-C₆ haloalkenyl; acetyl; CO₂Me; or N(C₁-C₂ alkyl)₂;

R¹⁵ is independently methyl; ethyl; methoxy; methylthio; halogen; or trifluoromethyl;

R¹⁶ is independently halogen; and

R¹⁷ is independently C₁-C₈ alkyl; or phenyl optionally substituted with at least one R¹³.

DETAILED DESCRIPTION OF THE INVENTION

In the above recitations, the term “alkyl”, used either alone or in compound words such as “alkythio,” “haloalkyl,” or “alkylthioalkyl” denotes straight-chain or branched alkyl; e.g.. methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl, hexyl, etc. isomers.

“Cycloalkyl” denotes cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term “cycloalkyloxyalkyl” denotes the cycloalkyl groups linked through an oxygen atom to an alkyl chain. Examples include cyclopentyloxymethyl and cyclohexyloxybutyl. The term “cycloalkylthioalkyl” are the cycloalkyl groups linked through a sulfur atom to an alkyl chain; e.g., cyclopropylthiopentyl. “Cycloalkylalkyl” denotes a cycloalkyl ring attached to a branched or straight-chain alkyl; e.g. cyclopropylmethyl and cyclohexylbutyl.

“Alkenyl” denotes straight chain or branched alkenes; e.g., 1-propenyl, 2-propenyl, 3-propenyl and the different butenyl, pentenyl, hexenyl, etc. isomers. Alkenyl also denotes polyenes such as 1,3-hexadiene and 2,4,6- heptatriene.

“Alkynyl” denotes straight chain or branched alkynes; e.g., ethynyl, 1-propynyl, 3-propynyl and the different butynyl, pentynyl, hexynyl, etc. isomers. “Alkynyl” can also denote moieties comprised of multiple triple bonds; e.g., 2,7-octadiyne and 2,5,8-decatriyne.

“Alkoxy” denotes methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy, hexyloxy, etc. isomers. “Alkoxyalkenyl” and “alkoxyalkynyl” denoted groups in which the alkoxy group is bonded throught the oxygen atom to an alkenyl or alkynyl group, respectively. Examples include CH₃OCH₂CH=CH and (CH₃)₂CHOCH₂C=CCH₂. The corresponding sulfur derivatives are denoted “alkylthioalkenyl” and “alkylthioalkynyl.” Examples of the former include CH₃SCH₂CH═CH and CH₃CH₂SCH₂(CH₃)CH═CHCH₂, and an example of the latter is CH₃CH₂CH₂CH₂SCH₂C═C.

“Alkenyloxy” denotes straight chain or branched alkenyloxy moieties. Examples of alkenyloxy include H₂C=CHCH₂O, (CH₃)₂C=CHCH₂O, (CH₃)CH=CHCH₂O, (CH₃)CH=C(CH₃)CH₂O and CH₂=CHCH₂CH₂O. “Alkenylthio” denotes the similar groups wherein the oxygen atom is replaced with a sulfur atom; e.g., H₂C=CHCH₂S and (CH₃)CH=C(CH₃)CH₂S. The term “alkenyloxyalkyl” denotes groups in which the alkenyloxy moiety is attached to an alkyl group. Examples include H₂C=CHCH₂OCH₂CH₂, H₂C=CHCH₂OCH(CH₃)CH₂, etc. “Alkenylthioalkyl” denotes the alkenylthio moieties bonded to an alkyl group. Examples include H₂C=CHCH₂SCH(CH₃)CH(CH₃) and (CH₃)CH=C(CH₃)CH₂SCH₂.

“Alkynyloxy” denotes straight or branched alkynyloxy moieties. Examples include HC≡CCH₂O, CH₃C≡CCH₂O and CH₃C≡CCH₂CH₂O. “Alkynyloxyalkyl” denotes alkynyloxy moieties bonded to alkyl groups; e.g., CH₃C≡CCH₂OCH₂CH₂ and HC≡CCH₂OCH(CH₃)CH₂. “Alkynylthioalkyl” denotes alkynylthio moieties bonded to alkyl groups. Example include CH₃≡CCH₂SCH₂CH₂ and CH₃C≡CCH₂CH₂SCH(CH₃)CH₂.

“Alkylthio” denotes methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. “Alkylthioalkyl” denotes alkylthio groups attached to an alkyl chain; e.g., CH₃CH₂SCH₂CH(CH₃) and (CH₃)₂CHSCH₂.

“Alkylsulfinyl” denotes both enantiomers of an alkylsulfinyl group. For example, CH₃S(O), CH₃CH₂S(O), CH₃CH₂CH₂S(O), (CH₃)₂CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsufinyl isomers. “Alkylsulfinylalkyl” denotes alkylsulfinyl groups attached to an alkyl chain; e.g., CH₃CH₂S(O)CH₂CH(CH₃) and (CH₃)₂CHS(O)CH₂.

Examples of “alkylsulfonyl” include CH₃S(O)₂, CH₃CH₂S(O)₂, CH₃CH₂CH₂S(O)₂. (CH₃)₂CHS(O)₂ and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. “Alkylsulfonylalkyl” denotes alkylsulfinyl groups attached to an alkyl chain: e.g. CH₃CH₂S(O)₂CH₂CH(CH₃) and (CH₃)₂CHS(O)₂CH₂.

The term “halogen” either alone or in compound words such as “haloalkyl”, denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F₃C, ClCH₂, CF₃CH₂ and CF₃CF₂. Examples of “haloalkenyl” include (Cl)₂C=CHCH₂ and CF₃CH₂CH=CHCH₂. “Haloalkenyloxyalkyl” denotes haloalkenyl groups bonded to oxygen and in turn bonded to alkyl groups. Examples include CF₃CH₂CH=CHCH₂OCH₂ and (Cl)₂C=CHCH₂OCH₂CH₂. Examples of “haloalkynyl” include HC≡CCHCl, CF₃C≡C, CCl₃C≡C and FCH₂C≡CCH₂. “Haloalkynyloxyalkyl” denotes haloalkynyl groups bonded through an oxygen atom to an alkyl moiety. Examples include CF₃C≡CCH₂OCH₂CH₂, ClCH₂C≡CCH₂CH₂OCH(CH₃), etc. Examples of “haloalkoxy” include CF₃O, CCl₃CH₂O, CF₂HCH₂CH₂O and CF₃CH₂O. “Haloalkoxyalkyl” denotes haloalkoxy groups bonded to straight-chain or branched alkyl groups; e.g., CF₂HCH₂CH₂OCH₂CH₂, CCl₃CH₂OCH(CH₃) and CF₃OCH₂.

“Trialkylsilyl” designates a group with three alkyl groups bonded to silicon; e.g., (CH₃)₃Si and t-Bu(CH₃)₂Si. “Trialkylsilylalkyl” denotes trialkylsilyl growups bonded to another straight-chain or branched alkyl group. Examples include (CH₃)₃SiCH₂ and t-Bu(CH₃)₂SiCH₂CH(CH₃)CH₂.

The total number of carbon atoms in a substituent group is indicated by the “C_(i)-C_(j)” prefix where i and j are numbers from 1 to 10. For example, C₁-C₃ alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C₂ alkoxyalkoxy designates CH₃OCH₂O; C₃ alkoxyalkoxy designates, for example, CH₃OCH₂CH₂O or CH₃CH₂OCH₂O; and C₄ alkoxyalkoxy designates the various isomers of an alkoxy group substituted with a second alkoxy group containing a total of 4 carbon atoms, examples including CH₃CH₂CH₂OCH₂O, and CH₃CH₂OCH₂CH₂O. Examples of “alkoxyalkyl” include CH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂.

Preferred for reasons of ease of synthesis or greater fungicidal activity are:

Preferred 1. The compounds of Formula I as defined above wherein:

Q is O;

R¹ is C₃-C₈ alkyl; C₄-C₈ alkenyl; C₄-C₈ alkynyl; C₁-C₈ haloalkyl; C₃-C₈ haloalkenyl: C₂-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₅-C₈ cycloalkylalkyl: C₂-C₈ alkyl substituted with cyano; C₁-C₈ alkoxy: C₁-C₈ haloalkoxy; C₁-C₈ alkylthio; or C₄-C₈ alkenyloxyalkyl; or pyridyl, furanyl, or thienyl each optionally substituted with R¹⁴ and R¹⁵;

R² is C₃-C₈ alkyl; C₁-C₈ alkenyl; C₃-C₈ alkynyl; C₁-C₈ haloalkyl; C₃-C₈ haloalkenyl; C₃-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₄-C₈ cycloalkylalkyl; C₃-C₈ cyanoalkyl; C₄-C₈ alkenyloxyalkyl; or phenyl optionally substituted with R¹³;

R³ is halogen; C₁-C₈ alkyl; C₂-C₈ alkynyl; C₃-C₈ cycloalkyl; C₁-C₈ haloalkyl; C₁-C₈ alkoxy; C₁-C₈ haloalkoxy; C₁-C₈ alkylthio; C₁-C₈ alkylsulfonyl; C₂-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₄-C₈ cycloalkylalkyl; or C₅-C₈ trialkylsilylalkyyl; and

R¹⁴ is methyl; ethyl; methoxy; ethoxy; C₁-C₂ haloalkyl; halogen; acetylenyl; propargyl; methylthio; ethylthio; cyano; nitro; C₁-C₂ haloalkoxy; vinyl; allyl; acetyl; CO₂Me; or N(C₁-C₂ alkyl)₂.

Preferred 2. The compounds of Formula II as defined above wherein:

Q is O;

n is 0;

R³ is halogen; C₁-C₈ alkyl; C₂-C₈ alkynyl; C₃-C₈ cycloalkyl; C₁-C₈ haloalkyl; C₁-C₈ alkoxy; C₁-C₈ haloalkoxy; C₁-C₈ alkylthio; C₁-C₈ alkylsulfonyl; C₂-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₄-C₈ cycloalkylkyl; or C₅-C₈ trialkylsilylalkynyl;

R⁵ is C₃-C₅ alkyl; C₄-C₇ alkynyl; C₃-C₅ alkynyl; C₁-C₈ haloalkyl; C₅-C₈ haloalkenyl; C₂-C₈ alkoxyalkyl other than methoxypropyl; C₂-C₈ alkylthioalkyl; C₄-C₈ cycloalkylalkyl; C₂-C₈ alkyl substituted with cyano; C₁-C₈ alkoxy; C₁-C₈ haloalkoxy; C₁-C₈ alkylithio; or C₄-C₈ alkenyloxyalkyl; or phenyl, furanyl, or thienyl each optionally substituted with R¹⁴ and R¹⁵;

R⁶ is C₃-C₈ alkyl; C₃-C₇ alkenyl; C₃-C₈ alkynyl; C₁-C₈ haloalkyl; C₃-C₃ haloalkenyl; C₃-C₈ alkoxyalkyl other than propoxymethyl; C₂-C₈ alkylthioalkyl; C₄-C₈ cycloalkylalkyl; C₅-C₈ cyanoalkyl; C₄-C₈ alkenyloxyalkyl; phenyl optionally substituted with R¹³; or C₃-C₅ alkyl substituted with phenyl optionally substituted with R¹³ and R¹⁵; and

R¹⁴ is methyl; ethyl; methoxy; ethoxy; C₁-C₂ haloalkyl; halogen; acetylenyl; propargyl; methylthio; ethylthio; cyano; nitro; C₁-C₂ haloalkoxy; vinyl; allyl; acetyl; CO₂Me; or N(C₁-C₂ alkyl)₂.

Preferred 3. The compounds of Formula m as defined above wherein:

Q is O;

R³ is halogen; C₁-C₈ alkyl; C₂-C₈ alknyl; C₃-C₈ cycloalkyl; C₁-C₈ haloalkyl; C₁-C₈ alkoxy; C₁-C₈ haloalkoxy; C₁-C₈ alkylthio; C₁-C₈ alkylsulfonyl; C₂-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₄-C₈ cycloalkylalkyl; or C₅-C₈ trialkylsilylalkynyl;

R⁷ is C₃-C₈ alkyl; C₄-C₇ alkenyl; propynyl; C₂-C₈ haloalkyl; C₃-C₈ haloalkenyl; C₂-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₂-C₈ alkyl substituted with cyano; C₁-C₈ alkoxy; C₁-C₈ haloalkoxy; C₁-C₈ alkylthio; or C₄-C₈ alkenyloxyalkyl; or phenyl, pyridyl, furanyl, or thienyl each optionally substituted with R¹⁴ and R¹⁵;

R⁹ is C₃-C₈ alkyl; C₃-C₈ alkenyl; C₃-C₈ alkynyl; C₃-C₈ haloalkyl; C₃-C₈ haloalkenyl; C₃-C₈ alkoxyalkyl; C₂-C₈ alkylthioalkyl; C₄-C₈ cycloalkylalkyl; C₄-C₈ cyanoalkyl; C₄-C₈ alkenyloxyalkyl; —NR¹²R¹⁷; or R³ and R⁴ are both iodine and R⁹ is phenyl optionally substituted with R¹⁴ and R¹⁵; and

R¹⁴ is methyl; ethyl; methoxy; ethoxy; C₁-C₂ haloalkyl; halogen; acetylenyl; propargyl; methylthio; ethylthio; cyano; nitro; C₁-C₂ haloalkoxy; vinyl; allyl; acetyl; CO₂Me; or N(C₁-C₂ alkyl)₂.

Preferred 4. The compounds of Preferreds 1, 2, and 3 wherein:

R¹ is C₃-C₈ alkyl; C₄-C₈ alkenyl; C₄-C₈ alkynyl; C₃-C₈ haloalkyl; C₃-C₈ haloalkenyl; C₃-C₈ alkoxyalkyl; or thienyl optionally substituted with at least one of R¹⁴ and R¹⁵;

R² is C₃-C₈ alkyl; C₃-C₈ alkenyl; C₃-C₈ alknyl; C₃-C₈ haloalkyl; C₃-C₈ haloalkenyl; C₃-C₈ alkoxyalkyl; or phenyl optionally substituted with R¹³;

R³ is halogen; C₁-C₄ alkyl; C₁-C₄ haloalkyl; C₁-C₄ alkoxy; C₁-C₄ haloalkoxy; acetylenyl; or trimethylsilylacetylenyl;

R⁵ is C₃-C₅ alkyl; C₄-C₇ alkenyl; C₃-C₅ alkynyl; C₃-C₈ haloalkyl; C₅-C₈ haloalkenyl; C₃-C₈ alkoxyalkyl; or phenyl or thienyl each optionally substituted with R¹⁴ and R¹⁵;

R⁶ is C₃-C₈ alkyl; C₃-C₇ alkenyl; C₃-C₈ alkyl; C₃-C₈ haloalkyl; C₃-C₈ haloalkenyl; C₃-C₈alkoxyalkyl; or phenyl optionally substituted with R¹³;

R⁷ is C₃-C₈ alkyl; C₄-C₇ alkenyl; propynyl; C₃-C₈ haloalkyl; C₃-C₈ haloalkenyl; C₃-C₈ alkoxy; C₃-C₈ alkoxyalkyl; or phenyl or thienyl each optionally substituted with R¹⁴ and R¹⁵;

R⁹ is C₃-C₈ alkyl; C₃-C₈ alkenyl; C₃-C₈ alkynyl; C₃-C₈ haloalkyl; C₃-C₈ haloalkenyl; C₃-C₈ alkoxyalkyl; —NR¹²R¹⁷; or R³ and R⁴ are both iodine and R⁹ is phenyl optionally substituted with R ¹⁴ and R¹⁵; and

R¹⁴ is methyl; ethyl; methoxy; methylthio; halogen; trifluoromethyl; or N(C₁-C₂ alkyl)₂.

Preferred 5. The compounds of Preferred 4 wherein:

R¹ is C₃-C₈ alkyl; C₄-C₈ alkenyl; C₄-C₈ alkynyl; C₃-C₈ haloalkyl; or C₃-C₈ haloalkenyl;

R² is C₃-C₈ alkyl; C₃-C₈ alkenyl; C₃-C₈ alkynyl; C₃-C₈ haloalkyl; C₃-C₈ haloalkenyl; or phenyl optionally substituted with R¹³;

R³ is halogen;

R⁴ is hydrogen or halogen;

R⁵ is C₃-C₅ alkyl; C₄-C₇ alkenyl; C₃-C₅ alkynyl; C₃-C₈ haloalkyl; or C₅-C₈ haloalkenyl; or phenyl optionally substituted with R¹⁴ and R¹⁵;

R⁶ is C₃-C₈ alkyl; C₃-C₇ alkenyl; C₃-C₈ alkynyl; C₃-C₈ haloalkyl; C₃-C₈ haloalkenyl; or phenyl optionally substituted with R¹³;

R⁷ is C₃-C₈ alkyl; C₄-C₇ alkenyl; propynyl; C₃-C₈ haloalkyl; or C₃-C₈ haloalkenyl; or phenyl optionally substituted with R¹⁴ and R¹⁵; and

R⁹ is C₃-C₈ alkyl; C₃-C₈ alkenyl; C₃-C₈ alkynyl; C₃-C₈ haloalkyl; C₃-C₈ haloalkenyl; —NR¹²R¹⁷; or R³ and R⁴ are both iodine and R⁹ is phenyl optionally substituted with R¹⁴ and R¹⁵.

Preferred 6. The compounds of Preferred 5 wherein said compounds are selected from the group:

6-bromo-3-propyl-2-propyloxy-4(3H)-quinazolinone;

6,8-diiodo-3-propyl-2-propyloxy-4(3H)-quinazoline;

6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone; and

6,8-diiodo-3-propyl-2(phenylamino)-4(3H)-quinazolinone.

It is recognized that some reagents and reaction conditions described below for preparing compounds of Formulae I, II, and III may not be compatible with some functionalities claimed for R¹-R¹⁷, n, m, and Q. In these cases, the incorporation of protection/deprotection sequences into the synthesis may be necessary in order to obtain the desired products. The cases in which protecting groups are necessary, and which protecting group to use, will be apparent to one skilled in chemical synthesis. See Greene, T. W. and Wuts, P. G. M.; Protective Groups in Organic Synthesis, 2nd Ed.; John Wiley & Sons, Inc.; New York, (1980) for suitable protecting groups.

In the following description of the preparation of compounds of Formulae I, II, and III, compounds of Formulae Ia and Ib, IIa-IIc, and IIIa-IIIe are various subsets of the compounds of Formulae I, II, and III. All substituents in compounds of Formulae Ia and Ib, IIa-IIc, and IIIa-IIIe and 2-7 are as defined above for Formulae I, II, and III.

Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active than the others and how to separate said stereoisomers. Accordingly, the present invention comprises mixtures, individual stereoisomers, and optically active mixtures of compounds of Formulae I, II, and III as well as agriculturally suitable salts thereof.

The compounds of Formulae I, II, and III can be prepared as described below in Schemes 1-9 and Examples 1-3.

Synthesis of Compounds of Formula I

Compounds of Formula Ia, compounds of Formula I wherein Q is O, can be made by the method illustrated in Scheme 1.

An anthranilic acid (2-aminobenzoic acid) of Formula 2 is condensed with an isothiocyanate of Formula R¹-NCS to form the 2-thioquinazolinedione of Formula 3. This condensation is preferably performed in the presence of a base such as triethylamine. S-Methylation of this compound affords the 2-methylthio-4(3H)-quinazolinone of Formula 4.

For the introduction of the R²O group, the 2-methylthio-4(3H)-quinazolinone of Formula 4 is treated with a mixture of a base, for example sodium hydride, in R²OH solvent. The reaction mixture is stirred at a temperature from about 0° C. to 120° C. for 1-120 hours. The desired 2-R²O-4(3H)-quinazolinone can be isolated from the reaction mixture by extraction into a water-immiscible solvent, and purified by chromatography or recrystallization. Similar synthetic procedures are described in U.S. Pat. No. 3,755,582, incorporated herein by reference.

Anthranilic acids of Formula 2 are known or can be prepared by known methods. For example see, March, J. Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985), p 983. The isothiocyanates of Formula R¹-NCS can be prepared from the corresponding amine by treatment with thiophosgene as known in the art. For example, see J. Heterocycl. Chem., (1990), 27,407.

Alternatively, 2-thioquinazolinediones of Formula 3 can be prepared by treatment of the (C₁-C₄ alkyl) anthranilic acid ester of Formula 5 with thiophosgene to form the isothiocyanate ester, followed by treatment with an amine of formula R¹NH₂ (Scheme 2).

The anthranilic acid ester of Formula 5 is treated with thiophosgene at a temperature from about −20° C. to 100° C. for 1 to 48 hours optionally in an inert solvent. Often this reaction is performed in a biphasic mixture in the presence of a base, such as calcium carbonate, and an acid, such as aqueous hydrochloric acid. The resulting isothiocyanate may be isolated by extraction into a water-immiscible solvent, such as methylene chloride, followed by drying of the organic extracts and evaporation under reduced pressure. Alternatively, the isothiocyanate can be combined in situ with the amine of Formula H₂-NR¹ and stirred at about −20° C. to 50° C. for 0.1 to 24 hours. The desired 2-thioquinazolinediones of Formula 3 can be isolated from the reaction mixture by aqueous extraction, and purified by chromatography or recrystallization. Similar synthetic procedures are described in J. Heterocycl. Chem., (1990), 27,407.

Compounds of Formula Ib, compounds of Formula I wherein Q is S, can be prepared as illustrated in Scheme 3.

Treatment of the quinazolinone of Formula Ia with phosphorous pentasulfide or Lawesson's reagent [2,4-bis(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide] in an inert solvent such as dioxane at a temperature 0° C. to the reflux temperature of the solvent for 0.1 to 72 hours affords the quinazolinethione of Formula Ib. This procedure is described in the literature, for example see U.S. Pat. No. 3,755,582.

Syntheses of Compounds of Formula II

4(3H)-Quinazolinones of Formula IIa, compounds of Formula II wherein n is 0 and Q is O, can be prepared by a modification of the synthesis illustrated in Scheme 1. As illustrated in Scheme 4, the 2-thioquinazolinedione of Formula 6 is alkylated with R⁶-X wherein X is a typical leaving group such as Br, I, CH₃SO₃ (OMs), or (4-CH₃-Ph)SO₃ (OTs) to afford the 2-R⁶S-4(3H)-quinazolinone of Formula IIa. One or more equivalents of a base can be used to accelerate the process. Bases such as sodium hydroxide and sodium hydride are suitable.

Typically, the 2-thioquinazolinedione is dissolved or dispersed in an inert solvent such as dimethylformamide and treated with a base at a temperature from about −20° C. to 60° C. with a base. The reaction mixture may then be heated to just above ambient temperature to the reflux temperature of the solvent for 0.1 to 24 hours to effect deprotonation. After cooling, the reaction mixture is cooled and treated with R⁶-X and stirred for 0.1-24 hours at a temperature from about 20° C. to the reflux temperature of the solvent. The quinazolinone of Formula IIa can be isolated by extraction into a water-immiscble solvent, and purified by chromatography or recrystallization.

2-Thioquinazolinediones of Formula 6 are prepared as described above in Schemes 1 and 2 for 2-thioquinazolinediones of Formula 3.

4(3H)-Quinazolinones of Formula IIb, compounds of Formula II wherein Q is O and n is 1 or 2, can be prepared by oxidation of the corresponding —SR⁶ compound of Formula Ia using well-known procedures for oxidation of sulfar (Scheme 5). For example, see March, J. Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985), p 1089.

4(3H)-Quinazolinethiones of Formula IIc, compounds of Formula II wherein Q is S, can be prepared by treatment of the corresponding quinazolinone with phosphorous pentasulfide or Lawesson's reagent as described in U.S. Pat. No. 3;755,582 and above for compounds of Formula Ib (Scheme 6).

Synthesis of Compounds of Formula III

4(3H)-Quinazolinones of Formula IIIa, compounds of Formula III wherein Q is O, can be prepared by the method illustrated in Scheme 7. This method is described in detail in U.S. Pat. No. 3,867,384 and incorporated herein by reference.

One method of preparation of compounds of Formula IIIa is by treatment of a 2-methylthio-4(3H)-quinazolinone of Formula 7 (Z=SMe) with an excess of an amine of Formula HNR⁸R⁹ at about 150° C. to 175° C. A second method is to contact a 2-chloro-4(3H)-quinazolinone of Formula 7 (Z=Cl) with one equivalent of HNR⁸R⁹ and one equivalent of an acid scavenger, for example triethylamine, or with two equivalents of HNR⁸R⁹, at a temperature between 60° C. and 120° C. optionally in the presence of a solvent.

The preparation of compounds of Formula 7 wherein Z is SMe is described above and in U.S. Pat. No. 3,755,582. The synthesis of compounds of Formula 7 wherein Z is Cl is described in U.S. Pat. No. 3,867,384. Amines of Formula HNR⁸R⁹ are commercially available or can be prepared by well-known methods (March, J. Advanced Organic Chemistry; 3rd ed., John Wiley: New York, (1985), p 1153).

In addition to the methods described above, compounds of Formula Ia and IIa can be prepared by displacement of the 2-chlorine in the appropriate 4(3H)-quinazolinone, rather than by displacement of the 2-SCH₃ group (Scheme 1) or S-alkylation of the thiocarbonyl (Scheme 4).

As described above for compounds of Formula Ib and IIc, quinazolinethiones of Formula IIIb can be prepared by treatment of the corresponding quinazolinone with P₂S₅ or Lawesson's reagent (Scheme 8).

Alternatively, 4(3H)-quinazolinones and quinazolinethiones of Formulae IIId and IIIe, compounds of Formula III wherein R⁸=—C(=O)R¹², can be prepared by acylation of the corresponding quinazolinones or quinazolinethione wherein R⁸=H (Formula IIIc) as illustrated in Scheme 9.

The quinazolinones of Formula IIIc can be treated with an acylating agent of Formula R¹⁰C(=O)L wherein L is an appropriate leaving group such as chlorine or OC(=O)(H or C₁-C₄ alkyl). In a similar fashion, compounds of Formula III wherein R⁸ is —C(=O)NHR¹² (Formula IIIe) can be prepared by condensing quinazolinones of Formula IIIc with isocyanates of Formula R¹⁴N=C=O using well known procedures.

Salts of compounds of Formulae I, II, and III can be formed by treating the free base of the corresponding compound with strong acids such as hydrochloric or sulfuric acid. Salts can also be prepared by alkylation of a tertiary amine group in the molecule to form, for example, the trialkylammonium salt. N-Oxides of compounds of Formulae I. II, and III can be made by oxidizing the corresponding reduced nitrogen compound with a strong oxidizing agent such as meta-chloroperoxybenzoic acid.

EXAMPLE 1 Synthesis of 6-Bromo-3-propyl-2-propyloxy-4(3H)-quinazolinone

All reactions were conducted under a nitrogen atmosphere.

Step A

To a solution of 200 mL of ethanol containing 37 g of 2-amino-5-bromobenzoic acid was added dropwise 17.72 mL of n-propyl isothiocyanate with stirring. The mixture was heated at reflux for 8 h, allowed to cool to room temperature and stirred for approximately 60 h. The mixture was then cooled to approximately 5° C. and filtered to obtain 15.42 g of an off-white solid.

Step B

To a solution containing 15.4 g of the product of Step A dissolved in 100 mL of 10% propanolic sodium hydroxide was added 3.2 mL of iodomethane with stirring. The mixture was stirred at room temperature for 10 min, then heated at reflux for 1.5 h, and then allowed to cool to room temperature and stirred overnight. The reaction mixture was filtered to obtain 11.47 g of a white solid. The white solid was purified by column chromatography on silica gel eluting with hexane and then 9:1 hexane:ethyl acetate. Collection and evaporation of those fractions containing the least polar component (according to thin layer chromatography, 6:1 hexane/ethyl acetate mixture as the development solvent) yielded 6.55 g of a white solid, m.p. 97-99° C.

Step C

To 150 mL of propanol cooled to approximately −60° C. was added 0.83 g of 1 aH (60% active in oil) with stirring. To this mixture at −60° C. was added 6.5 g of the purified product obtained in Step B. The mixture was allowed to warm to room temperature and stirred for approximately 48 h to yield a clear solution. The reaction solution was poured into water and extracted twice with diethyl ether. The ether extracts were washed twice with water, dried over magnesium sulfate, filtered and the filtrate was then evaporated to yield 10.3 g of an oil. Thin layer chromatography indicated starting material and desired product were both present.

Step D

To propanol cooled to −50° C. was added 0.60 g of NaH (60% active in oil) with stirring. To this mixture at −40° C. was added the product of Step C and the mixture was allowed to warm to room temperature and stirred for approximately 72 h. The mixture was then heated at reflux for 30 min. cooled to room temperature, poured into water and extracted twice with diethyl ether. The combined ether extracts were washed three times with water, dried over magnesium sulfate, filtered and the filtrate was evaporated to yield an oil. The oil was purified by column chromatography on silica gel eluting with hexane followed by 9:1 hexane/ethyl acetate. Collection and evaporation of the fractions containing only the least polar component (according to thin layer chromatography on silica gel, 9:1 hexane/ethyl acetate mixture as the development solvent) yielded 4.46 g of the title compound as a white solid, m.p. 57-59° C: ¹H NMR (400 MHz, CDCl₃) δ 8.3 (s,1H), 7.7 (m,1H), 7.3 (m,1H), 4.43 (t,2H), 4.05 (t,2H), 1.85 (m,2H), 1.7 (m,2H), 1.06 (t,3H), 0.97 (t,3H).

EXAMPLE 2 Synthesis of 6-Bromo-3-n-butyl-2-n-propylamino-4(3H)-quinazolinone

Step A

To a solution of 200 mL of ethanol containing 15.15 g of 2-amino-5-bromobenzoic acid was added dropwise 9.3 mL of n-butyl isothiocyanate with stirring. To this reaction solution was added 9.77 mL of triethylamine. The reaction solution was heated at reflux for 4 h during which time a solid precipitated. The reaction mixture was cooled to 0° C. and filtered to obtain 19.89 g of an off-white solid, m.p. 246-248° C.

Step B

To a solution containing 7 g of the product of Step A suspended in 50 mL of chloroform was added 1.97 mL of sulfuryl chloride with stirring. The solution was heated at reflux for 5 h, then cooled to room temperature. The reaction solution was poured into water and extracted twice with methylene chloride. The organic extracts were dried over magnesium sulfate, filtered and the filtrate was then evaporated to a yellow solid. The solid was purified by column chromatography on silica gel eluting with 6:1 hexane/ethyl acetate. Collection and evaporation of the fractions containing only the second-least polar component (according to thin layer chromatography on silica gel, 4:1 hexane/ethyl acetate mixture as the development solvent) yielded 3.2 g of white solid. m.p. 56-58° C.

Step C

To a solution containing 1.02 g of the purified product obtained in Step B dissolved in 25 mL of tetrahydrofuran was added 0.5 mL of n-propylamine. The reaction mixture was stirred for approximately 24 h at room temperature. The reaction was then filtered and the filtrate was evaporated to obtain an oil. The oil was dissolved in diethyl ether and washed twice with water and once with brine. The ether solution was dried over magnesium sulfate, filtered and the filtrate was then evaporated to yield 0.74 g of the title compound as a white solid, m.p. 71-73° C: ¹H NMR (400 MHz, CDCl₃) 0.97-1.04 (m,6H). 1.45 (m,2H). 1.70 (m,4H), 3.50 (m,2H), 4.00 (t,2H), 4.50 (s,1H), 7.24 (d,1H), 7.60 (d,1H), 8.20 (s,1H).

EXAMPLE 3 Synthesis of 6-Bromo-3-n-propyl-2-n-propylthio-4(3H)-quinazolinone

Step A

To a solution of 150 mL isopropanol containing 29.7 g of 2-amino-5-bromobenzoic acid was added dropwise. 15.64 mL of n-propyl isothiocyanate with stirring. The reaction mixture was then heated at reflux for 15 h. The reaction mixture was cooled to 0° C. and filtered to obtain 9.12 g of an off-white solid.

Step B

To a solution containing 0.34 g of the product of Step A suspended in 20 mL of 10% propanolic sodium hydroxide was added 0.22 mL of iodopropane with stirring. The reaction mixture was stirred 1.5 h at room temperature. The reaction was poured into water and extracted twice with methylene chloride. The methylene chloride extractions were washed twice with water, dried over magnesium sulfate, filtered, and the filtrate was then evaporated to yield a white solid. The solid was purified by column chromatography on silica gel eluting with 8:1 hexane/ethyl acetate. Collections and evaporation of the fractions containing only the least-polar component (according to thin layer chromatography on silica gel, 6:1 hexane/ethyl acetate mixture as the development solvent) yielded 0.27 g of the title compound as a white solid, m.p. 65-67° C.: ¹H NMR (400 MHz, CDCl₃): δ0.99-1.10 (m,6H), 1.80 (m,4H), 3.25 (t,2H), 4.10 (t,2H), 7.41 (d,1H), 7.78 (d,1H), 8.30 (s,1H).

Using the procedures outlined in Schemes 1-9 and Examples 1-3, the compounds of Tables 1-12 hereinafter can be prepared. The compounds referred to in the Tables which follow are illustrated below:

The following abbreviations are used in the Tables which follow . All alkyl groups are the normal isomers unless indicated otherwise. See structures in Index Tables A-C hereinafter for ring system numbering.

t = tertiary MeO = methoxy s = secondary Pr = propyl n = normal CN = cyano i = iso c = cyclo Me = methyl MeS = methylthio Et = ethyl Bu = butyl Ph = phenyl

TABLE 1 R¹ R¹ R¹ R¹ Compounds of Formula I wherein: Q = O, R² = n-Pr, R³ = 6-Br, R⁴ = H, and n-Pr n-Bu n-pentyl n-hexyl n-decyl i-Pr i-Bu s-Bu c-propyl c-butyl c-pentyl 2-butenyl 3-butenyl 2-butynyl 3-butynyl CF₃ 2-Cl-Et 3-Br-Pr CH₂CH═CHCl CH₂C≡CCl CH₂OCH₃ CH₂OCH₂CH₃ CH₂SCH₃ CH₂SCH₂CH₃ CH₂CH₂SCH₃ CH₂CH₂S(O)CH₃ CH₂CH₂CH₂S(O)₂CH₃ (c-pentyl)CH₂ CH₂CH₂OCH₂CH═CH₂ CH₂CH₂OCH₂CH≡CH (c-hexyl)OCH₂ (c-pentyl)SCH₂ CH₂CH₂SCH₂CH═CH₂ CH₂CH₂SCH₂CH≡CH CH₂OCF₃ CH₂OCH₂CH₂Cl CH₂OCH₂CH═CHCl CH₂OCH₂C≡CBr CH₂CH═CHCH₂OCH₃ CH₂C≡CCH₂OCH₃ CH₂CH═CHCH₂SCH₃ CH₂C≡CCH₂SCH₃ CH₂CH₂Si(CH₃)₃ CH₂CH₂N(CH₃)₂ CH₂CH₂CH₂NHCH₃ CH₂CH₂NO₂ CH₂CH₂CH₂CN PhCH₂ OCH₂CH₂CH₃ OCH₂CH₂CF₃ SCH₂CH₃ SCCl₃ SCH₂CH₂Cl NHCH₂CH₂CH₃ N(CH₃)CH₂CH₃ Ph 2-pyridinyl 2-furanyl 2-thienyl 2-naphthyl 5-benzofuranyl 3-benzothienyl 3-quinolinyl (4-F-Ph)CH₂ Compounds of Formula I wherein: Q = O, R² = n-Pr, R³ ⁼ 6-I, R⁴ = H, and n-Pr n-Bu n-pentyl n-hexyl n-decyl i-Pr i-Bu s-Bu c-propyl c-butyl c-pentyl 2-butenyl 3-butenyl 2-butynyl 3-butynyl CF₃ 2-Cl-Et 3-Br-Pr CH₂CH═CHCl CH₂C≡CCl CH₂OCH₃ CH₂OCH₂CH₃ CH₂SCH₃ CH₂SCH₂CH₃ CH₂CH₂SCH₃ CH₂CH₂S(O)CH₃ CH₂CH₂CH₂S(O)₂CH₃ (c-pentyl)CH₂ CH₂CH₂OCH₂CH═CH₂ CH₂CH₂OCH₂C≡CH (c-hexyl)OCH₂ (c-pentyl)SCH₂ CH₂CH₂SCH₂CH═CH₂ CH₂CH₂SCH₂C≡CH CH₂OCF₃ CH₂OCH₂CH₂Cl CH₂OCH₂CH═CHCl CH₂OCH₂C≡CBr CH₂CH═CHCH₂OCH₃ CH₂C≡CCH₂OCH₃ CH₂CH═CHCH₂SCH₃ CH₂C≡CCH₂SCH₃ CH₂CH₂Si(CH₃)₃ CH₂CH₂N(CH₃)₂ CH₂CH₂CH₂NHCH₃ CH₂CH₂NO₂ CH₂CH₂CH₂CN (4-F-Ph)CH₂ OCH₂CH₂CH₃ OCH₂CH₂CF₃ SCH₂CH₃ SCCl₃ SCH₂CH₂Cl NHCH₂CH₂CH₃ N(CH₃)CH₂CH₃ PhCH₂ 2-pyridinyl 2-furanyl 2-thienyl 2-naphthyl 5-benzofuranyl 3-benzothienyl 3-quinolinyl (2-Me-Ph)CH₂CH₂ Compounds of Formula I wherein: Q = O, R² = n-Pr, R³ = 6-I, R⁴ = 8-1, and n-Pr n-Bu n-pentyl n-hexyl n-decyl i-Pr i-Bu s-Bu c-propyl c-butyl c-pentyl 2-butenyl 3-butenyl 2-butynyl 3-butynyl CF₃ 2-Cl-Et 3-Br-Pr CH₂CH═CHCl CH₂C≡CCl CH₂OCH₃ CH₂OCH₂CH₃ CH₂SCH₃ CH₂SCH₂CH₃ CH₂CH₂SCH₃ CH₂CH₂S(O)CH₃ CH₂CH₂CH₂S(O)₂CH₃ (c-pentyl)CH₂ CH₂CH₂OCH₂CH═CH₂ CH₂CH₂OCH₂C≡CH (c-hexyl)OCH₂ (c-pentyl)SCH₂ CH₂CH₂SCH₂CH═CH₂ CH₂CH₂SCH₂C≡CH CH₂OCF₃ CH₂OCH₂CH₂Cl CH₂OCH₂CH═CHCl CH₂OCH₂C≡CBr CH₂CH═CHCH₂OCH₃ CH₂C≡CCH₂OCH₃ CH₂CH═CHCH₂SCH₃ CH₂C≡CCH₂SCH₃ CH₂CH₂Si(CH₃)₃ CH₂CH₂N(CH₃)₂ CH₂CH₂CH₂NHCH₃ CH₂CH₂NO₂ CH₂CH₂CH₂CN PhCH₂ OCH₂CH₂CH₃ OCH₂CH₂CF₃ SCH₂CH₃ SCCl₃ SCH₂CH₂Cl NHCH₂CH₂CH₃ N(CH₃)CH₂CH₃ (2-Me-Ph)CH₂CH₂ 2-pyridinyl 2-furanyl 2-thienyl 2-naphthyl 5-benzofuranyl 3-benzothienyl 3-quinolinyl (4-F-Ph)CH₂

TABLE 2 R² R² R² R² Compounds of Formula I wherein: Q = O, R¹ = n-Pr, R³ = 6-Br, R⁴ = H, and CH₂CH₂CH₂F t-Bu i-Pr n-Bu i-Bu s-Bu n-pentyl n-hexyl n-decyl c-hexyl allyl 2-butenyl 3-butenyl 5-decenyl propargyl 2-butynyl 3-butynyl CF₃ CH₂CF₃ CH₂CH═CHCl CH₂C≡CBr CH₂OCH₃ CH₂OCH₂CH₃ CH₂CH₂OCH₃ CH₂SCH₃ CH₂CH₂SCH₃ CH₂CH₂CH₂S(O)₂CH₃ (c-pentyl)CH₂ 2-Cl-Et CH₂CH₂OCH₂C≡CH CH₂CH₂SCH₂CH═CH₂ (c-propyl)OCH₂ (c-hexyl)SCH₂ CH₂CH₂OCF₃ CH₂CH₂SCH₂C≡CH CH₂CH₂CH₂CN CH₂CH₂Si(CH₃)₃ —NHPh CH₂CH₂OCH₂CCl═CH₂ CH₂OCH₂CH₂Cl CH₂(4-F-Ph) —N(CH₃)Ph CH₂CH₂CH₂N(CH₃)₂ CH₂CH₂CH₂Ph CH₂CH₂CH₂F CH₂Ph CH₂CH₂OCH₂CH═CH₂ CH₂CH₂Ph CH₂CH₂CH₂NHCH₃ CH₂CH₂NO₂ —N═CHPh CH₂CH₂(4-F-Ph) —N═CHCH₂CH₂CH₃ —N═C(CH₃)₂ NHCH₂CH₂CH₃ N(CH₃)₂ Compounds of Formula 1 wherein: Q = O, R¹ = n-Pr, R³ = 6-I, R⁴ = H, and CH₂CH₂CH₂F t-Bu i-Pr n-Bu i-Bu s-Bu n-pentyl n-hexyl n-decyl c-hexyl allyl 2-butenyl 3-butenyl 5-decenyl propargyl 2-butynyl 3-butynyl CF₃ CH₂CF₃ CH₂CH═CHCl CH₂C≡CBr CH₂OCH₃ CH₂OCH₂CH₃ CH₂CH₂OCH₃ CH₂SCH₃ CH₂CH₂SCH₃ CH₂CH₂CH₂S(O)₂CH₃ (c-pentyl)CH₂ 2-Cl-Et CH₂CH₂OCH₂C≡CH CH₂CH₂SCH₂CH═CH₂ (c-propyl)OCH₂ (c-hexyl)SCH₂ CH₂CH₂OCF₃ CH₂CH₂SCH₂C≡CH CH₂CH₂CH₂CN CH₂CH₂Si(CH₃)₃ CH₂CH₂CO₂Et CH₂CH₂OCH₂CCl═CH₂ CH₂OCH₂CH₂Cl Ph 4-Me-Ph CH₂CH₂CH₂N(CH₃)₂ 2-F-Ph 4-MeO-Ph CH₂Ph CH₂CH₂OCH₂CH═CH₂ CH₂CH₂Ph CH₂CH₂CH₂NHCH₃ CH₂CH₂NO₂ —N═CHPh CH₂CH₂(4-F-Ph) —N═CHCH₂CH₂CH₃ —N═C(CH₃)₂ NHCH₂CH₂CH₃ N(CH₃)₂ 2,4-diCl-Ph 2,4,6-triF-Ph 4-CF₃-Ph 2-CN-Ph CH₂(4-F-Ph) —NHPh —N(CH₃)Ph CH₂CH₂CH₂Ph Compounds of Formula I wherein: Q = O, R¹ = n-Pr, R³ = 6-I, R⁴ = 8-I, and CH₂CH₂CH₂F t-Bu i-Pr n-Bu i-Bu s-Bu n-pentyl n-hexyl n-decyl c-hexyl allyl 2-butenyl 3-butenyl 5-decenyl propargyl 2-butynyl 3-butynyl CF₃ CH₂CF₃ CH₂CH═CHCl CH₂C≡CBr CH₂OCH₃ CH₂OCH₂CH₃ CH₂CH₂OCH₃ CH₂SCH₃ CH₂CH₂SCH₃ CH₂CH₂CH₂S(O)₂CH₃ (c-pentyl)CH₂ 2-Cl-Et CH₂CH₂OCH₂C≡CH CH₂CH₂SCH₂CH═CH₂ (c-propyl)OCH₂ (c-hexyl)SCH₂ CH₂CH₂OCF₃ CH₂CH₂SCH₂C≡CH CH₂CH₂CH₂CN CH₂CH₂Si(CH₃)₃ CH₂CH₂CO₂Et CH₂CH₂OCH₂CCl═CH₂ CH₂OCH₂CH₂Cl Ph 4-Me-Ph CH₂CH₂CH₂N(CH₃)₂ 2-F-Ph 4-MeO-Ph CH₂Ph CH₂CH₂OCH₂CH═CH₂ CH₂CH₂Ph CH₂CH₂CH₂NHCH₃ CH₂CH₂NO₂ —N═CHPh CH₂CH₂(4-F-Ph) —N═CHCH₂CH₂CH₃ —N═C(CH₃)₂ NHCH₂CH₂CH₃ N(CH₃)₂ 2,4-diCl-Ph 2,4,6-triF-Ph 4-CF₃-Ph 2-CN-Ph CH₂(4-F-Ph) —NHPh —N(CH₃)Ph CH₂CH₂CH₂Ph

TABLE 3 Compounds of Formula I wherein Q = O and R¹ = R² = n-Pr, and R³ R⁴ R³ R⁴ R³ R⁴ 6-Cl H 6-Me H 6-Me₃Si 8-Br 6-Br 8-Me 6-Et 8-Br 6-Me₂N H 6-I 8-Br 6-MeO H 6-EtNH H 6-Cl 8-Cl 6-MeS 8- 6-Br 8-Me MeO 6-Br 8-Cl 6-SCH₂CH═CH₂ H 6-Br 8-Et 6-I 8-I 6-S(O)₂Me H 6-i-Pr H 6-C≡CH H 6-Br 8- 6-Br 8- CF₃ OCF₃ 6-C≡CH 8-Br 6-CH₂C≡CH H 6-CF₃O H 6-c-propyl H 6-Br 7-Br 6-CH≡CH₂ H 6-CF₃ H 6-OCH₂CH═CH₂ H 6-Br 7-Me 6-CH₂Br H 6-Br Me 6-Br 5-Br 6-CH═CHBr H 6-(c-propyl)CH₂ H 8-Br H 6-CH₃OCH₂ H 6-I 8-Me 6-Me 8-Br

TABLE 3 Compounds of Formula I wherein Q = O and R¹ = R² = n-Pr, and R³ R⁴ R³ R⁴ R³ R⁴ 6-Cl H 6-Me H 6-Me₃Si 8-Br 6-Br 8-Me 6-Et 8-Br 6-Me₂N H 6-I 8-Br 6-MeO H 6-EtNH H 6-Cl 8-Cl 6-MeS 8- 6-Br 8-Me MeO 6-Br 8-Cl 6-SCH₂CH═CH₂ H 6-Br 8-Et 6-I 8-I 6-S(O)₂Me H 6-i-Pr H 6-C≡CH H 6-Br 8- 6-Br 8- CF₃ OCF₃ 6-C≡CH 8-Br 6-CH₂C≡CH H 6-CF₃O H 6-c-propyl H 6-Br 7-Br 6-CH≡CH₂ H 6-CF₃ H 6-OCH₂CH═CH₂ H 6-Br 7-Me 6-CH₂Br H 6-Br Me 6-Br 5-Br 6-CH═CHBr H 6-(c-propyl)CH₂ H 8-Br H 6-CH₃OCH₂ H 6-I 8-Me 6-Me 8-Br

TABLE 3 Compounds of Formula I wherein Q = O and R¹ = R² = n-Pr, and R³ R⁴ R³ R⁴ R³ R⁴ 6-Cl H 6-Me H 6-Me₃Si 8-Br 6-Br 8-Me 6-Et 8-Br 6-Me₂N H 6-I 8-Br 6-MeO H 6-EtNH H 6-Cl 8-Cl 6-MeS 8- 6-Br 8-Me MeO 6-Br 8-Cl 6-SCH₂CH═CH₂ H 6-Br 8-Et 6-I 8-I 6-S(O)₂Me H 6-i-Pr H 6-C≡CH H 6-Br 8- 6-Br 8- CF₃ OCF₃ 6-C≡CH 8-Br 6-CH₂C≡CH H 6-CF₃O H 6-c-propyl H 6-Br 7-Br 6-CH≡CH₂ H 6-CF₃ H 6-OCH₂CH═CH₂ H 6-Br 7-Me 6-CH₂Br H 6-Br Me 6-Br 5-Br 6-CH═CHBr H 6-(c-propyl)CH₂ H 8-Br H 6-CH₃OCH₂ H 6-I 8-Me 6-Me 8-Br

TABLE 6 R⁶ R⁶ R⁶ R⁶ Compounds of Formula II wherein: Q = O, n = 0, R⁵ = n-Pr, R³ = 6-Br, R⁴ = H, and CH₂C(CH₃)═CH₂ t-Bu i-Pr n-Bu i-Bu s-Bu n-pentyl n-hexyl n-decyl CH₂CH(CH₃)CH₂CH₃ allyl 2-butenyl 3-butenyl 5-heptenyl propargyl 2-butynyl 3-butynyl CF₃ CH₂CF₃ CH₂CH═CHCl CH₂C≡CBr CH₂CH₂O(CH₂)₂CH₃ CH₂OCH₂CH₃ CH₂CH₂OCH₃ CH₂SCH₃ CH₂CH₂SCH₃ CH₂CH₂CH₂S(O)₂CH₃ (c-pentyl)CH₂ 2-Cl-Et CH₂CH₂OCH₂C≡CH CH₂CH₂SCH₂CH═CH₂ (c-propyl)OCH₂ (c-hexyl)SCH₂ CH₂CH₂OCF₃ CH₂CH₂SCH₂C≡CH (CH₂)₄CN CH₂CH₂Si(CH₃)₃ CH₂CH₂CH₂CO₂Et CH₂CH₂OCH₂CCl═CH₂ CH₂OCH₂CH₂Cl Ph 4-Me-Ph CH₂CH₂CH₂N(CH₃)₂ 2-F-Ph 4-MeO-Ph (CH₂)₄Ph CH₂CH₂OCH₂CH═CH₂ CH₂CH₂CH₂Ph CH₂CH₂CH₂NHCH₃ CH₂CH₂NO₂ —N═CHPh CH₂CH₂(4-F-Ph) 4-Cl-Ph 2-Me-Ph NHCH₂CH₂CH₃ N(CH₃)₂ 2,4-diCl-Ph 2,4,6-triF-Ph 4-CF₃-Ph 2-CN-Ph —NHPh —N(CH₃)Ph CH₂CH₂CH₂(4-F-Ph) Compounds of Formula II wherein: Q = O, n = 0, R⁵ = n-Pr, R³ = 6-I, R⁴ = H, and CH₂C(CH₃)═CH₂ t-Bu i-Pr n-Bu i-Bu s-Bu n-pentyl n-hexyl n-decyl CH₂CH(CH₃)CH₂CH₃ allyl 2-butenyl 3-butenyl 5-heptenyl propargyl 2-butynyl 3-butynyl CF₃ CH₂CF₃ CH₂CH═CHCl CH₂C≡CBr CH₂CH₂O(CH₂)₂CH₃ CH₂OCH₂CH₃ CH₂CH₂OCH₃ CH₂SCH₃ CH₂CH₂SCH₃ CH₂CH₂CH₂S(O)₂CH₃ (c-pentyl)CH₂ 2-Cl-Et CH₂CH₂OCH₂C≡CH CH₂CH₂SCH₂CH═CH₂ (c-propyl)OCH₂ (c-hexyl)SCH₂ CH₂CH₂OCF₃ CH₂CH₂SCH₂C≡CH (CH₂)₄CN CH₂CH₂Si(CH₃)₃ CH₂CH₂CH₂CO₂Et CH₂CH₂OCH₂CCl═CH₂ CH₂OCH₂CH₂Cl Ph 4-Me-Ph CH₂CH₂CH₂N(CH₃)₂ 2-F-Ph 4-MeO-Ph CH₂Ph CH₂CH₂OCH₂CH═CH₂ CH₂CH₂CH₂Ph CH₂CH₂CH₂NHCH₃ CH₂CH₂NO₂ —N═CHPh CH₂CH₂CH₂(4-F-Ph) 4-Cl-Ph 2-Me-Ph NHCH₂CH₂CH₃ N(CH₃)₂ 2,4-diCl-Ph 2,4,6-triF-Ph 4-CF₃-Ph 2-CN-Ph —NHPh —N(CH₃)Ph

TABLE 7 Compounds of Formula II wherein Q = O, n = 0, R⁵ = R⁶ = n-Pr, and R³ R⁴ R³ R⁴ R³ R⁴ 6-Cl H 6-Me H 6-Me₃Si 8-Br 6-Br 8-Me 6-Et 8-Br 6-Me₂N H 6-I 8-Br 6-MeO H 6-EtNH H 6-Cl 8-Cl 6-MeS 8-MeO 6-Br 8-Me 6-Br 8-Cl 6-SCH₂CH═CH₂ H 6-Br 8-Et 6-I 8-I 6-S(O)₂Me H 6-i-Pr H 6-C≡CH H 6-Br 8-CF₃ 6-Br 8- OCF₃ 6-C≡CH 8-Br 6-CH₂C≡CH H 6-CF₃O H 6-c-propyl H 6-Br 7-Br 6-CH≡CH₂ H 6-CF₃ H 6- H 6-Br 7-Me OCH₂CH═CH₂ 6-CH₂Br H 6-Br Me 6-Br 5-Br 6-CH═CHBr H 6-(c- H 8-Br H propyl)CH₂ 6-MeOCH₂ H 6-I 8-Me 6-Me 8-Br

TABLE 7 Compounds of Formula II wherein Q = O, n = 0, R⁵ = R⁶ = n-Pr, and R³ R⁴ R³ R⁴ R³ R⁴ 6-Cl H 6-Me H 6-Me₃Si 8-Br 6-Br 8-Me 6-Et 8-Br 6-Me₂N H 6-I 8-Br 6-MeO H 6-EtNH H 6-Cl 8-Cl 6-MeS 8-MeO 6-Br 8-Me 6-Br 8-Cl 6-SCH₂CH═CH₂ H 6-Br 8-Et 6-I 8-I 6-S(O)₂Me H 6-i-Pr H 6-C≡CH H 6-Br 8-CF₃ 6-Br 8- OCF₃ 6-C≡CH 8-Br 6-CH₂C≡CH H 6-CF₃O H 6-c-propyl H 6-Br 7-Br 6-CH≡CH₂ H 6-CF₃ H 6- H 6-Br 7-Me OCH₂CH═CH₂ 6-CH₂Br H 6-Br Me 6-Br 5-Br 6-CH═CHBr H 6-(c- H 8-Br H propyl)CH₂ 6-MeOCH₂ H 6-I 8-Me 6-Me 8-Br

TABLE 7 Compounds of Formula II wherein Q = O, n = 0, R⁵ = R⁶ = n-Pr, and R³ R⁴ R³ R⁴ R³ R⁴ 6-Cl H 6-Me H 6-Me₃Si 8-Br 6-Br 8-Me 6-Et 8-Br 6-Me₂N H 6-I 8-Br 6-MeO H 6-EtNH H 6-Cl 8-Cl 6-MeS 8-MeO 6-Br 8-Me 6-Br 8-Cl 6-SCH₂CH═CH₂ H 6-Br 8-Et 6-I 8-I 6-S(O)₂Me H 6-i-Pr H 6-C≡CH H 6-Br 8-CF₃ 6-Br 8- OCF₃ 6-C≡CH 8-Br 6-CH₂C≡CH H 6-CF₃O H 6-c-propyl H 6-Br 7-Br 6-CH≡CH₂ H 6-CF₃ H 6- H 6-Br 7-Me OCH₂CH═CH₂ 6-CH₂Br H 6-Br Me 6-Br 5-Br 6-CH═CHBr H 6-(c- H 8-Br H propyl)CH₂ 6-MeOCH₂ H 6-I 8-Me 6-Me 8-Br

TABLE 10 R⁹ R⁹ R⁹ R⁹ Compounds of Formula III wherein: Q = O, R⁷ = n-Pr, R⁸ = H, R³ = 6-Br, R⁴ = H, and Et t-Bu i-Pr n-Bu i-Bu s-Bu n-pentyl n-hexyl n-decyl CH₂CH(CH₃)CH₂CH₃ allyl 2-butenyl 3-butenyl 5-heptenyl propargyl 2-butynyl 3-butynyl CH₂CH₂CH₂Cl CH₂CH₂CF₃ CH₂CH═CHCl CH₂C≡CBr CH₂CH₂O(CH₂)₂CH₃ CH₂OCH₂CH₃ CH₂CH₂OCH₃ CH₂SCH₃ CH₂CH₂SCH₃ CH₂CH₂CH₂S(O)₂CH₃ (c-pentyl)CH₂ 2-Cl-Et CH₂CH₂OCH₂C≡CH CH₂CH₂SCH₂CH═CH₂ (c-propyl)OCH₂ (c-hexyl)SCH₂ CH₂CH₂OCF₃ CH₂CH₂SCH₂C≡CH (CH₂)₃CN CH₂CH₂Si(CH₃)₃ CH₂CH₂CH₂CO₂Et CH₂CH₂OCH₂CCl═CH₂ CH₂OCH₂CH₂Cl —N═CHPh —NHPh CH₂CH₂CH₂N(CH₃)₂ c-propyl c-hexyl —NC(═O)NHPh CH₂CH₂OCH₂CH═CH₂ —N(═S)NHPh CH₂CH₂CH₂NHCH₃ CH₂CH₂NO₂ —NHCH₂CH₂CH₃ N(CH₃)₃ ⁺I⁻ —N═CHCH₂CH₂CH₃ —N═C(CH₃)₂ NHCH₂CH₂CH₃ N(CH₃)₂ —OCH₂CH₂CH₃ (CH₂)₃(2,4,6-triF-Ph) CH₂(4-CF₃-Ph) —OCH₂CH(CH₃)₂ Compounds of Formula III wherein: Q = O, R⁷ = n-Pr, R⁸ = H, R³ = 6-I, R⁴ = H, and Et t-Bu i-Pr n-Bu i-Bu s-Bu n-pentyl n-hexyl n-decyl CH₂CH(CH₃)CH₂CH₃ allyl 2-butenyl 3-butenyl 5-heptenyl propargyl 2-butynyl 3-butynyl CH₂CH₂CH₂Cl CH₂CH₂CF₃ CH₂CH═CHCl CH₂C≡CBr (CH₂)₂OCH₂CH₃ CH₂OCH₂CH₃ CH₂CH₂OCH₃ CH₂SCH₃ CH₂CH₂SCH₃ CH₂CH₂CH₂S(O)₂CH₃ (c-pentyl)CH₂ 2-Cl-Et CH₂CH₂OCH₂C≡CH CH₂CH₂SCH₂CH═CH₂ (c-propyl)OCH₂ (c-hexyl)SCH₂ CH₂CH₂OCF₃ CH₂CH₂SCH₂C≡CH (CH₂)₃CN CH₂CH₂Si(CH₃)₃ CH₂CH₂CO₂Et CH₂CH₂OCH₂CCl═CH₂ CH₂OCH₂CH₂Cl —N═CHPh —NC(═O)NHPh CH₂CH₂CH₂N(CH₃)₂ c-propyl c-hexyl CH₂CH₂NO₂ CH₂CH₂OCH₂CH═CH₂ —N(═S)NHPh CH₂CH₂CH₂NHCH₃ CH₂CH₂NO₂ —NHCH₂CH₂CH₃ N(CH₃)₃ ⁺I⁻ —N═CHCH₂CH₂CH₃ —N═C(CH₃)₂ NHCH₂CH₂CH₃ N(CH₃)₂ —OCH₂CH₂CH₃ (CH₂)₃(2,4,6-triF-Ph) CH₂(4-CF₃-Ph) —OCH₂CH(CH₃)₂ Compounds of Formula III wherein: Q = O, R⁷ = n-Pr, R⁸ = H, R³ = 6-I, R⁴ = H, and Et t-Bu i-Pr n-Bu i-Bu s-Bu n-pentyl n-hexyl n-decyl CH₂CH(CH₃)CH₂CH₃ allyl 2-butenyl 3-butenyl 5-heptenyl propargyl 2-butynyl 3-butynyl CH₂CH₂CH₂Cl CH₂CH₂CF₃ CH₂CH═CHCl CH₂C≡CBr (CH₂)₂OCH₂CH₃ CH₂OCH₂CH₃ CH₂CH₂OCH₃ CH₂SCH₃ CH₂CH₂SCH₃ CH₂CH₂CH₂S(O)₂CH₃ (c-pentyl)CH₂ 2-Cl-Et CH₂CH₂OCH₂C≡CH CH₂CH₂SCH₂CH═CH₂ (c-propyl)OCH₂ (c-hexyl)SCH₂ CH₂CH₂OCF₃ CH₂CH₂SCH₂C≡CH (CH₂)₃CN CH₂CH₂Si(CH₃)₃ CH₂CH₂CO₂Et CH₂CH₂OCH₂CCl═CH₂ CH₂OCH₂CH₂Cl —N═CHPh —NHPh CH₂CH₂CH₂N(CH₃)₂ c-propyl c-hexyl —NC(═O)NHPh CH₂CH₂OCH₂CH═CH₂ —N(═S)NHPh CH₂CH₂CH₂NHCH₃ CH₂CH₂NO₂ —NHCH₂CH₂CH₃ N(CH₃)₃ ⁺I⁻ —N═CHCH₂CH₂CH₃ —N═C(CH₃)₂ NHCH₂CH₂CH₃ N(CH₃)₂ —OCH₂CH₂CH₃ (CH₂)₃(2,4,6-triF-Ph) CH₂(4-CF₃-Ph) —OCH₂CH(CH₃)₂ Ph 4-F-Ph 2-Me-Ph 2,4-diCl-Ph

TABLE 11 Compounds of Formula III wherein Q = O, R⁸ = H, R⁷ = R⁹ = n-Pr, and R³ R⁴ R³ R⁴ R³ R⁴ 6-Cl H 6-Me H 6-Me₃Si 8-Br 6-Br 8-Me 6-Et 8-Br 6-Me₂N H 6-I 8-Br 6-MeO H 6-EtNH H 6-Cl 8-Cl 6-MeS 8-MeO 6-Br 8-Me 6-Br 8-Cl 6-SCH₂CH═CH₂ H 6-Br 8-Et 6-I 8-I 6-S(O)₂Me H 6-i-Pr H 6-C≡CH H 6-Br 8-CF₃ 6-Br 8- OCF₃ 6-C≡CH 8-Br 6-CH₂C≡CH H 6-CF₃O H 6-c-propyl H 6-Br 7-Br 6-CH═CH₂ H 6-CF₃ H 6- H 6-Br 7-Me OCH₂CH═CH₂ 6-CH₂Br H 6-Br 5-Me 6-Br 5-Br 6-CH═CHBr H 6-(c-propyl)CH₂ H 8-Br H 6-MeOCH₂ H 6-I 8-Me 6-Me 8-Br

TABLE 11 Compounds of Formula III wherein Q = O, R⁸ = H, R⁷ = R⁹ = n-Pr, and R³ R⁴ R³ R⁴ R³ R⁴ 6-Cl H 6-Me H 6-Me₃Si 8-Br 6-Br 8-Me 6-Et 8-Br 6-Me₂N H 6-I 8-Br 6-MeO H 6-EtNH H 6-Cl 8-Cl 6-MeS 8-MeO 6-Br 8-Me 6-Br 8-Cl 6-SCH₂CH═CH₂ H 6-Br 8-Et 6-I 8-I 6-S(O)₂Me H 6-i-Pr H 6-C≡CH H 6-Br 8-CF₃ 6-Br 8- OCF₃ 6-C≡CH 8-Br 6-CH₂C≡CH H 6-CF₃O H 6-c-propyl H 6-Br 7-Br 6-CH═CH₂ H 6-CF₃ H 6- H 6-Br 7-Me OCH₂CH═CH₂ 6-CH₂Br H 6-Br 5-Me 6-Br 5-Br 6-CH═CHBr H 6-(c-propyl)CH₂ H 8-Br H 6-MeOCH₂ H 6-I 8-Me 6-Me 8-Br

Formulation/Utility

Compounds of this invention will generally be used in formulation with an agriculturally suitable composition. The fungicidal compositions of the present invention comprise an effective amount of at least one compound of Formula I, II, or III as defined above and at least one of (a) a surfactant, (b) an organic solvent, and (c) at least one solid or liquid diluent. Useful formulations can be prepared in conventional ways. They include dusts, granules, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation. The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up 100 weight percent.

Weight Percent Active Ingredient Diluent Surfactant Wettable Powders 5-90  0-74 1-10 Oil Suspensions, Emulsions, 5-50 40-95 0-15 Solutions, (including Emulsifiable Concentrates) Dusts 1-25 70-99 0-5  Granules, Baits and Pellets 0.01-99      5-99.99 High Strength Compositions 90-99   0-10 0-2 

Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, N.J. Typical liquid diluents and solvents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, (1950). McCurcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, N.J., as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, (1964), list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth, and the like.

Methods for formulating such compositions are well known. Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill. Water-dispersible granules can be produced by agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., (1988), pp 251-259. Suspensions are prepared by wet-milling; see, for example, U.S. Pat. No. 3,060,084. Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, “Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp 147-148, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, (1963), pp 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. Pat. No. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in DE 3,246,493.

For further information regarding the art of formulation, see U.S. Pat. No. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10 through 41; U.S. Pat. No. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12,15,39,41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, (1961), pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, (1989).

In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound 1 refers to the compound described in Index Table A hereinafter.

Example A Wettable Powder Compound 1 65.0% dodecylphenol polyethylene glycol ether  2.0% sodium ligninsulfonate  4.0% sodium silicoaluminate  6.0% montmorillonite (calcined)  23.0%. Example B Granule Compound 37 10.0% attapulgite granules (low volative  90.0%. matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) Example C Extruded Pellet Compound 25 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate  5.0% sodium alkylnaphthalenesulfonate  1.0% calcium/magnesium bentonite  59.0%. Example D Emulsifiable Concentrate Compound 37 20.0% blend of oil soluble sulfonates 10.0% and polyoxyethylene ethers isophorone  70.0%.

The compounds of this invention are useful as plant disease control agents, especially for the control of cereal powdery mildews (e.g., Erysiphe graminis f. sp. tritici, the causal agent of wheat powdery mildew). The present invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, or to the plant seed or seedling to be protected, an effective amount of a compound of Formula I, II, or III or a fungicidal composition containing said compound. The compounds and compositions of this invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and Deuteromycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Alternaria brassicae, Septoria nodorum, Cercosporidium personatum, Cercospora arachidicola, Pseudocercosporella herpotrichoides, Cercospora bericola, Bortrytis cinerea, Monilinia fructicola, Pyricularia oryzae, Podosphaera leucotricha, Venturia inaequalis, Erysiphe graminis, Uncinula necatur, Puccinia recondita, Puccinia graminis, Hemileia vastatrix, Puccinia striiformis, Puccinia arachidis, Rhizoctonia solani, Sphaerotheca fuliginea, Fusarium oxysporum, Verricillium dahliae, Pythium aphanidermatum, Phytophthora megasperma and other generea and species closely related to these pathogens.

Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, semiochemicals, repellants, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Examples of other agricultural protectants with which compounds of this invention can be formulated are: insecticides such as acephate, avermectin B, azinphosmethyl, bifenthrin, biphenate, buprofezin, carbofuran, chlordimeform, chlorpyrifos, cyfluthrin, deltamethrin, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenpropathrin, fenvalerate, fipronil, flucythrinate, flufenprox, fluvalinate, fonophos, isofenphos, malathion, metaldehyde, metha-midophos, methidathion, methomyl, methoprene, methoxychlor, monocrotophos, oxamyl, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, rotenone, sulprofos, terbufos, tetrachlorvinphos, thiodicarb, tralomethri, triclorfon and triflumuron; fungicides such as benomyl, blasticidin S, bromuconazole, captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts, cymoxanil, cyproconazole, cyrodinil, dichloran, diclobutrazol, diclomezine, difenoconazole, diniconazole, dodine, edifenphos, epoxyconazole fenaritnol, fenbuconazole, fenpropidine, fenpropinorph, fluquinconazole, flusilazol, flutolanil, flutriafol, folpet, furalaxyl, hexaconazole, ipconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin, mancozeb, maneb, mepronil, metalaxyl, metconazole, myclobutanil, neo-asozin, oxadixyl, penconazole, pencycuron, phosethyl-Al, probenazole, prochloraz, propiconazole, pyrifenox, pyrimethanil, pyroquilon, sulfur, tebuconazole, tetraconazole, thiabendazole, thiophanate-methyl, thiuram, triadimefon, triadinenol, tricylazole, triticonazole, uniconzole, validamycin and vinclozolin; nematocides such as aldoxycarb, fenamiphos and fosthietan; bactericides such as oxytetracyline, streptomycin and tribasic copper sulfate; acaricides such as amitraz, binapacryl, chlorobenzilate, cyhexatin, dicofol, dienochlor, fenbutatin oxide, hexythiazox, oxythioquinox, propargite and tebufenpyrad; and biological agents such as Bacillus thuringiensis and baculovirus.

In certain instances, combinations with other fungicides having a similiar spectrum of control but a different mode of action will be particularly advantageous for resistance management. Preferred combinations comprise a compound of Formula I, II, or III, and a fungicide selected from the group flusilazole, cyproconazole, tetraconazole, fenpropimorph, fenpropidine, cymoxanil, benomyl, carbendazim, mancozeb, and maneb.

Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compounds can also be applied to the seed to protect the seed and seedling.

Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 g/ha to 5,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed.

The following TESTS demonstrate the control efficacy of compounds of this invention on specific pathogens. The pathogen control protection afforded by the compounds is not limited, however, to these species. See Index Tables A, B, and C for compound descriptions.

Test-compounds were first dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concerion of 200 ppm in purified water containing 250 ppm of the surfactant Trem® 014(polyhydric alcohol esters). The resulting test suspensions were then used in the following tests.

TEST A

The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore dust of Erysiphe graminis f. sp. tritici, (the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20° C. for 7 days, after which disease ratings were made.

TEST B

The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Puccinia recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20° C. for 24 h, and then moved to a growth chamber at 20° C. for 6 days, after which disease ratings were made.

TEST C

The test suspension was sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Phytophthora infestans (the causal agent of potato and tomato late blight) and incubated in a saturated atmosphere at 20° C. for 24 h, and then moved to a growth chamber at 20° C. for 5 days, after which disease ratings were made.

TEST D

The test suspension was sprayed to the point of run-off on grape seedlings. The following day the seedlings were inoculated with a spore suspension of Plasmopara viticola (the causal agent of grape downy mildew) and incubated in a saturated atmosphere at 20° C. for 24 h. moved to a growth chamber at 20° C. for 6 days, and then incubated in a saturated atmosphere at 20° C. for 24 h. after which disease ratings were made.

TEST E

The test suspension was sprayed to the point of run-off on cucumber seedlings. The following day the seedlings were inoculated with a spore suspension of Botrytis cinerea (the causal agent of gray mold on many crops) and incubated in a saturated atmosphere at 20° C. for 48 h, and moved to a growth chamber at 20° C. for 5 days, after which disease ratings were made.

In the Tables below, a=¹H NMR data for oils are listed in Index Table D

INDEX TABLE A Ia

Compounds of Formula Ia: Cmpd No. R¹ R² R³ R⁴ m.p.^(a)(° C.)  1 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-Br H 57-59  2 CH₂CH₂CH₃ CH₂CH₂CH₃ 7-Cl H 57-60  3 CH₂CH₂CH₃ CH₂CH₂CH₃ 5-O H 69-75  4 CH₂CH₂CH₃ CH₂CH₂CH₃ 8-Me H 47-49  5 CH₂CH₂CH₃ CH₂CH₂CH₃ 5-Me H Oil  6 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-Me H 47-50  7 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-OMe 7-OMe 112-114  8 CH₂CH₂CH₃ CH₂CH₂CH₃ 7-F H oil  9 CH₂CH₂CH₃ CH₂CH₂CH₃ 7-NO2 H 64-66 10 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-OMe H 4-2 11 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-Me 8-Me 81-84 12 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-C≡CH H 105-107 13 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-F H 60-62 14 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-Cl H 64-66 15 CH₂CH₂CH₃ CH₂CH═CH₂ 6-Cl H 78-80 16 CH₂CH₂CH₃ CH₂CH═CH₂ 6-Br H 73-75 17 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-Cl 8-Cl 78-80 18 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-Br 8-Br 89-94 22 CH₂CH₂CH₃ (CH₂)₃CH₃ 6-Br H 58-59 23 CH₂CH₂CH₃ i-Pr 6-Br H 45-46 25 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-I H 48-49 26 CH₂CH₂CH₃ (CH₂)₄CH₃ 6-Br H 56-57 27 CH₂CH₂CH₃ (CH₂)₅CH₃ 6-Br H oil 28 CH₂CH₂CH₃ i-Pr 6-Cl H 48-49 29 (CH₂)₃CH₃ CH₂CH₂CH₃ 6-Br H 56-58 30 CH₂CH₂CH₃ CH₂CH₂CH═CH₂ 6-Cl H oil 31 CH₂CH₂CH₃ CH₂CH₂C(CH₃)₃ 6-Br H 70-72 32 CH₂CH₂CH₃ (CH₂)₃CH₂SCH₃ 6-Br H 86-91 33 CH₂CH₂CH₃ CH₂CH₂CH═CH₂ 6-Br H oil 34 CH₂CH₂CH₃ (CH₂)₄CH₃ 6-Cl H oil 35 CH₂CH₂CH₃ (CH₂)₄CH₃ 6-I H 47-49 36 CH₂CH₂CH₃ CH₂CH₂CH═CH₂ 6-I H 43-46 37 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-I 8-I 135-138 38 (CH₂)₃CH₃ (CH₂)₃CH₃ 6-Br H oil 39 CH₂CH₂CH₃ (CH₂)₂CH₂Ph 6-Br H 72-74 40 CH₂CH₂CH₃ CH₂CH₂OCH₃ 6-Br H 55-57 41 CH₂CH₂CH₃ CH₂CH₂N(CH₃)2 6-Br H 39-42 42 CH₂CH₂CH₃ CH₂CH₂N(CH₃)2HCl 6-Br H 215-230 43 (CH₂)₃N(CH₃)2 CH₂CH₂CH₃ 6-Br H oil 44 (CH₂)₃OCH₃ CH₂CH₂CH₃ 6-Br H 61-64 45 CH₂CH(CH₃)2 CH₂CH₂CH₃ 6-Br H 50-55 46 (c-propyl)CH₂ CH₂CH₂CH₃ 6-Br H  99-101 47 CH(CH₃)Et CH₂CH₂CH₃ 6-Br H oil 48 (CH₂)₄CH₃ (CH₂)₄CH₃ 6-Br H oil 49 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-NO2 H 68-75 50 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-C≡C—SiMe₃ H 76-78 51 CH₂CH₂CH₃ CH₂CH₂CH₂CH₃ 6-I H 54-57 52 (CH₂)₃CH₃ (CH₂)₃CH₃ 6-I H 50-51 53 (CH₂)₃CH₃ CH₂CH₂CH₃ 6-I H 50-52 54 (CH₂)₃SCH₃ CH₂CH₂CH₃ 6-Br H 69-71 55 CH₂CH₂CH₃ CH₂CH₂N⁺(CH₃)₃I⁻ 6-Br H 223-225 56 (CH₂)₃N⁺(CH₃)₃I⁻ CH₂CH₂CH₃ 6-Br H 200-204 57 (CH₂)₃N(CH₃)2HCl CH₂CH₂CH₃ 6-Br H 145-150 58 CH₂CHBrCH₂Br CH₂CH₂CH₃ 6-Br H 118-121 59 CH₂CH₂(N-1,4-morpholinyl) CH₂CH₂CH₃ 6-Br H 103-105

INDEX TABLE B IIa

Compounds of Formula IIa: Cmpd No. R⁵ R⁶ R³ R⁴ m.p.(° C.) 60 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-I H 90-92 61 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-Br H 65-67

INDEX TABLE B IIa

Compounds of Formula IIa: Cmpd No. R⁵ R⁶ R³ R⁴ m.p.(° C.) 60 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-I H 90-92 61 CH₂CH₂CH₃ CH₂CH₂CH₃ 6-Br H 65-67

Index Table D Cmpd No. ¹H NMR Data^(b)  5 7.46 (dd,1H), 7.29 (d,1H), 7.04 (d,1H), 4.42 (t,2H), 4.02 (m,2H), 2.84 (s.3H), 1.85 (m,2H), 1.71 (m,2H), 1.06 (t,3H), 0.98 (t,3H).  8 8.17 (dd,1H), 7.09 (dd,1H), 7.00 (dt,1H), 4.43 (t,2H), 4.05 (m,2H), 1.85 (m,2H), 1.73 (m,2H), 1.07 (t,3H), 0.97 (t,3H). 27 0.93-0.99 (2-t,6H), 1.37 (m,4H), 1.48 (m,2H), 1.75 (m,2H), 1.80 (m,2H), 4.05 (t,2H), 4.46 (t,2H), 7.34 (d,1H), 7.70 (d,1H), 8.30 (s,1H). 30 0.94-0.98 (t,3H), 1.70 (m,2H), 2.59 (m,2H), 4.02 (t,2H), 4.53 (t,2H), 5.19 (dd,2H), 5.90 (m,1H), 7.40 (d,1H), 7.59 (d,1H), 8.12 (s,1H). 33 0.93-0.98 (t,3H), 1.70 (m,2H), 2.60 (q,2H), 4.03 (t,2H), 4.51-4.55 (t,2H), 5.20 (dd,2H), 8.29, 8.30 (m,1H). 34 0.95-0.99 (m,6H), 1.41 (m,4H), 1.70 (m,2H), 1.81 (m,2H), 4.05 (t,2H), 4.44-4.48 (t,2H), 7.40 (d,1H), 7.58 (d,1H), 8.13 (s,1H). 38 0.94-1.03 (2-t,6H), 1.40 (m,2H), 1.48 (m,2H), 1.65 (m,2H), 1.80 (m,2H), 4.10 (t,2H), 4.47 (t,2H), 7.34 (d,1H), 7.70 (d,1H), 8.29 (s,1H). 43 2.22 (s,6H), 7.33 (d,1H), 7.71 (d,1H), 8.30 (s,1H). 47 1.45 (d,3H), 7.30 (d,1H), 7.68 (d,1H), 8.29 (s,1H). 48 7.31 (d,1H), 7.69 (d,1H),8.30 (s,1H). 63 0.88-0.92 (m,9H), 1.59 (m,4H), 1.75 (m,2H), 3.09-3.13 (t,4H), 4.08 (t,2H), 7.38 (d,1H), 7.70 (d,1H), 8.30 (s,1H). 70 0.99 (m,6H), 1.44 (m,4H), 1.66 (m,2H), 3.53 (q,2H), 4.00 (t.2H), 4.49 (s,1H), 7.25 (d,1H), 7.61 (d 1H), 8.10 (s,1H). 72 8.40 (s,1H), 7.89 (d,1H), 7.10 (d,1H), 4.50 (s,1H), 4.0 (t,2H), 3.53 (q,2H), 1.68 (m,4H), 1.45 (m,4H), 0.96-1.01 (m,6H). 73 8.40 (s,1H), 7.79 (d,1H), 7.10 (d,1H), 4.52 (s,1H), 4.0 (t,2H), 3.49 (q.2H), 1.70 (m.4H), 1.43 (m,2H), 0.96-1.02 (m,6H). ^(b)Unless indicated otherwise. ¹H NMR spectra were obtained in CDCl₃ on a 400 MHz spectrometer. Data are reported in ppm downfield from tetramethylsilane; s = singlet, d = doublet, t = triplet, m = multiplet, dd = doublet of doublets, dt = doublet of triplets.

Results for Tests A-E are given in Table 13. In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls). “−” =not tested.

TABLE 13 Test Test Test Test Test Cmpd No. A¹ B C D E 1 100 4 24 58 0 2 75 7 0 18 0 3 72 59 0 92 0 4 41 3 0 26 0 5 54 0 23 50 0 6 45 0 0 0 81 7 7 57 23 50 0 8 14 3 0 26 0 9 96 0 0 39 0 10 40 0 0 17 67 12 100 0 0 91 83 13 95² 0 0 0 0 14 100 0 0 41 45 15 99³ 0 0 41 4 16 100³ 0 0 41 0 17 99³ 0 33 0 0 18 100³ 20 20 0 32 22 100 0 0 41 0 23 97 46 0 0 0 25 100³ 46 0 8 0 26 — 4¹ 0 6 0 27 100 7 0 18 0 29 97 46 0 0 0 30 100³ 3 0 26 0 31 38 3 0 26 0 32 100³ 3 0 26 0 33 100 3 0 81 0 34 100³ 3 0 68 0 35 100³ 0 0 0 0 36 100³ 3 0 50 0 37 100³ 93 26 13 0 38 100³ 54 66 99 0 39 99³ 0 0 16 0 40 100³ 54 100 16 0 41 100 0 23 41 0 42 — 0 23 0 0 43 100³ 62 45 62 0 44 100³ 62 0 0 0 45 100³ 0 0 0 67 46 100³ 0 0 17 0 47 50¹ 0 0 0 0 48 92³ 61 0 0 0 49 36 16 0 56 0 50 99³ 0 0 56 0 51 100³ 4 0 56 63 52 100³ 57 0 10 36 53 100³ 4 0 83 36 54 95 43 0 10 0 55 59³ 81 0 74 0 56 57³ 92 0 17 0 57 91 12 23 99 37 58 98 — — — — 59 100 56 0 8 0 60 — 0 0 7 0 61 100³ 15 0 33 65 62 99 83 19 98 28 63 97 0 42 100 28 64 100³ 76 43 0 0 65 100³ 23² 0 96 44 66 99 0 0 0 0 67 89³ 7 0 18 0 68 100³ 0 26 13 0 69 94 79 80 89 0 70 97 63 0 100 0 71 100³ 57 0 56 63 72 100³ 4 0 91 63 73 100 57 0 72 63 76 99³ 16 21 9 0 77 99 52 44 100 68 79 97² 6 0 39 0 80 100³ 57 0 56 0 ¹Test was run at 10 ppm unless otherwise indicated. ²Test was run at 40 ppm. ³Test was run at 2 ppm. 

What is claimed is:
 1. A fungicidal compound of Formula II for controlling wheat powdery mildew

selected from the group consisting of (1) compounds wherein Q is O, n is 0, R⁵ is n-Pr, n-Bu, i-Pr, n-pentyl, i-Bu, or s-Bu, R⁶ is n-Pr, R⁴ is H and R³ is 6-Br or 6-I; (2) compounds wherein Q is O, n is 0, R⁵ is n-Pr, R⁶ is i-Bu, t-Bu, s-Bu, i-Pr, n-pentyl, n-Bu or n-hexyl, R⁴ is H and R³ is 6-Br or 6-I; and (3) compounds wherein Q is O, n is 0, R⁵ and R⁶ are both n-Pr, and R³ is 6-I and R⁴ is 8-Br or 8-I, R³ is 6-Cl and R⁴ is 8-Cl or hydrogen, R³ is 6-Br and R⁴ is 8-Cl, 5-Br, 7-Br or 8-Br, or R³ is 8-Br and R⁴ is H.
 2. The fungicidal compound for controlling wheat powdery mildew of claim 1 which is 6-bromo-3-propyl-2-propylthio-4(3H)-quinazolinone.
 3. A fungicidal composition for controlling wheat powdery mildew comprising an effective amount of a compound of Formula II

wherein: Q is O; n is 0; R³ is halogen; R⁴ is hydrogen or halogen; R⁵ is C₃-C₅ alkyl; and R⁶ is C₃-C₈ alkyl and at least one of (a) a surfactant, (b) an organic solvent and (c) at least one solid or liquid diluent.
 4. A method of controlling wheat powdery mildew comprising applying to the plant or portion thereof to be protected, to the media in which the plant to be protected is growing, or to the plant seed or seedling to be protected an effective amount of a compound of Formula II

wherein: Q is O; n is 0; R³ is halogen; R⁴ is hydrogen or halogen; R⁵ is C₃-C₅ alkyl; and R⁶ is C₃-C₈ alkyl.
 5. The method for controlling wheat powdery mildew of claim 4 wherein 6-bromo-3-propyl-2-propylthio-4(3H)-quinazolinone is applied. 